The present invention relates to filters for the purification of liquids. In particular the invention relates to the production and antimicrobial treatment of sintered porous thermoplastic filters used for the purification of liquids, for the protection of such filters from microbial growth and for the purification of liquids treated by them with respect to microbial and other dissolved and undissolved contaminants.
Sintered porous filters made from thermoplastic materials are used extensively in treating potable water and other fluids to remove particulate and dissolved contaminants. (See U.S. Pat. No. 6,030,558; U.S. Pat. No. 4,797,243; U.S. Pat. No. 5,547,481; EPO Patent 743,085A2; and EPO Patent Application 659,482A1) Sintering is a process of compressing powdered thermoplastics in a mold at temperatures just below their melting point. Powdered particles are fused together but the mass, as a whole does not melt. These sintered materials are used as filters since they can be made to have specific porosity. These filters are typically made by fusing discrete particles of selected thermoplastic polymers under elevated temperature and pressure conditions while enclosed in a mold. These thermoplastic polymers typically have a low melt flow rate, which means that at their melting point they have a very high viscosity which minimizes the flow of the melted mass. When heated, the polymer particles fuse at the point of contact, creating a solidified porous body with a complex pore structure and with good mechanical strength. It is necessary that the particles retain their shape, save for the slight softening at the point of contact where fusing occurs as the temperature is reduced from the elevated temperatures to near ambient levels. Particle shape retention can occur only when the melt flow rate of the polymer is low. The melt flow rate is defined by the so-called Melt Index, which is a measure of the amount of material that is extruded from a small orifice during a period of 10 minutes at 43.5 psi of pressure. Sintering temperatures of 374 F. (190 C.) and 446 F. (230 C.) are specified for polyethylene and polypropylene respectively. (ASTM Method-D-1238). A high melt index material indicates a low-viscosity polymer. Melt Index is calculated and given as grams per 10 min. Low melt index is usually achieved when the molecular weight of the polymer is high. One of the most suitable thermoplastic polymers used for these filters is High Density Polyethylene (HDPE) with a molecular weight approaching one million. So-called Ultra High Density Polyethylenes have molecular weights of one million or more and have melt indices of 0.0 to 0.5.
Any thermoplastic polymer meeting the desired low melt index conditions can be used for filter applications, including, without limitation, polypropylene, polyethylene, polysulfone, polyethersulfone, polyphenylene sulfide, ethylene vinyl acetate and the like. Typically, any thermoplastic polymer can be irradiated with either gamma rays or X-rays to induce cross-linking within it, which results in an increase in its molecular weight and which decreases its melt flow rate. Typically, sintered porous filters are made with predetermined particle size, which determines the size of its pores; i.e., the finer the size of the original particle, the finer is the average size of the pore in the sintered product. In fluid filtration applications, sintered filters have average pore sizes from 5 microns to 100 microns. The original size of the thermoplastic particle to produce these pore sizes in the filter is from 40 to 800 microns. More typically, the particle size is from 75 to 300 microns. Besides the size of the original particles, the porosity of the sintered filter can also be controlled by using blends of high and low melt flow materials. In this case, high melt polymers determine the average pore size, while the low melt polymer gives the filter its structural strength. Besides using blends of similar and dissimilar polymers with high and low melt flow rate, it is also possible to add other types of particulate materials in the matrix that impart other properties to the filter structure. For instance it is possible to embed activated carbon, synthetic ion exchange resins, inorganic and organic adsorption media such as metal oxides, modified peat, etc., in the sintered product (See EP Patent 0,659,482A1). The resultant filter then has the added capability to adsorb volatile organic substances such as pesticides, inorganic dissolved ions such as calcium, lead, mercury, arsenic and nitrates, etc., besides its traditional function to remove particulate materials.
Although the science and art of making sintered filters with various capabilities to remove particulate material and dissolved organic and inorganic impurities from fluid is well established, there is still a paucity of technology to protect these sintered porous filters from microbial growth. Trapped microorganisms are able to proliferate in these filters, creating serious health hazards, especially in the field of drinking water and where the filters are used in the processing of materials for human consumption such as food. The growth of microorganisms within the filter also reduces flow through the filter and requires higher operating pressures and/or frequent filter replacement. One of the technologies to prevent the growth of microorganism uses iodinated synthetic ion exchange resin embedded in sintered thermoplastic porous filter (See EP 0,659,482 A1xe2x80x9cIon exchange resin sintered in porous matrixxe2x80x9d by Edward C. Giordano and Hans-Gunther Sternagel) Here antimicrobial action depends on slow release of iodine ions. While this method is acceptable to the U.S. Environmental Protection Agency (EPA) on a temporary or emergency basis to purify drinking water, its prolonged usage is not approved by the EPA because of the adverse effect of iodine on human health. In other known technology a synthetic ion exchange resin or other material such as activated carbon can be treated with silver and then subsequently embedded in the porous sintered thermoplastic filter. This method of treatment suffers from very high cost and also by the fact that silver surfaces become deactivated when exposed to water containing dissolved chlorine or chloride ions.
Applicant is aware of the following U.S. Patents and European Patent Office publications concerning the use of sintered porous filters made from thermoplastic materials.
The present invention provides an effective way to prevent the growth of microorganisms within a sintered porous filter by incorporating in it an antimicrobial agent that is practically insoluble in the fluid passing through the filter, and is safe, nontoxic, non-carcinogenic, non-sensitizing to human and animal skin, and does not accumulate in the human body when ingested. Furthermore this antimicrobial is a broad spectrum antimicrobial agent, i.e., it is equally effective against the majority of harmful bacteria encountered in water and food. For example, an antimicrobial agent such as 2,4,4xe2x80x2-trichloro-2xe2x80x2-hydroxydiphenol ether, or 5-chloro-2-phenol (2,4 dichlorophenoxy) commonly sold under the trademark Microban Additive B, by Microban Products Company, Huntersville, N.C., typically will be used. However, it will be understood that various other antimicrobial agents that are safe, non-toxic, and substantially insoluble in water or a fluid in question can be used in the present invention.
During normal operation, the antimicrobial agent is incorporated into a second thermoplastic material having an equal or higher melt flow rate than the first thermoplastic, but preferably a higher melt flow rate. Preferably, the porosity and the homogeneous distribution of antimicrobial agent is achieved by using blends of high and low melt flow material.
The present invention incorporates antimicrobial treatment of sintered porous thermoplastic filters used in purification of liquids, firstly to protect these filters from microbial growth within the filter (Bactriostasis), making it a source of added contamination, and secondly for the microbial treatment of liquids as they pass through these filters (Bacteriocidal). A unique feature of this invention is the achievement of the above objectives in a cost-effective manner using antimicrobial additives that do not pose any danger to human beings or to the environment.
The essence of this invention is a filter having porosity provided by the interstices between the particles, with an additional surface of thermoplastic particles on the basic particles, the additional surface of thermoplastic particles having an antimicrobial agent incorporated therein which in no way affects the sintering process that creates the matrix of porosity in the filter. The particles of the thermoplastic polymer are still able to melt and fuse at the point of contact during sintering, creating a stable rigid porous structure. This is achieved by introducing the antimicrobial agent as a concentrate in another chemically and physically compatible thermoplastic polymer that has substantially the same, but preferably higher, melt flow rate compared to the main thermoplastic polymer. Preferably, the melt flow rate of thermoplastic polymer containing homogeneously distributed antimicrobial additive is sufficiently high that it wets the surface of main thermoplastic particles and becomes uniformly distributed over the entire surface, except for the fused points of contact. Care must be exercised in choosing the difference between the melt flow rates so that the extreme differences in the flow properties do not lead to incomplete coverage of the particle surfaces with the antimicrobial additive. If there are extreme differences in the melting temperatures as well as in the melt flow rates of the two polymers, there will be separation of these polymers that will result in inhomogeneous and inconsistent distribution of antimicrobial additive within the porous structure.
A porous sintered filter produced under the optimum conditions of this invention creates a matrix of bonded solid particles and pores where the antimicrobial additive uniformly and substantially continuously covers the surfaces, although some gaps in coverage can be tolerated. By either choosing the particle size of the thermoplastic that is within the specified range or by combination of low and high melt flow polymers, it is possible to create a very tortuous path for the liquid flowing therethrough so that microorganisms are forced to encounter the antimicrobial surfaces during their path and become deactivated. Thus, even though the pores of these filters are greater than 5 micron, the filters are still effective in deactivating the much smaller microorganisms that pass through them. As a result, it is possible to treat water or other fluids through this filter to reduce the concentration of microorganisms by greater than 99%.
The invented sintered porous thermoplastic filter may have embedded therein materials such as activated carbon, synthetic ion exchange resins, inorganic media which adsorb perchlorates, nitrates, calcium, or heavy metals such as lead, mercury, arsenic, chromium, etc. Of special note is that the invented filter provides protection of activated carbon and synthetic ion exchange resins, which are otherwise prone to attack by bacteria, which would create high counts of bacteria in the filter and in the fluid effluent.
The antimicrobial additive is preferably 2,4,4xe2x80x2-trichloro-2xe2x80x2-hydroxydiphenol ether, or 5-chloro-2phenol(2,4 dichlorophenoxy), which is commonly manufactured and sold under the trademark MICROBAN Additive B, by Microban Products Company, Huntersville, N.C., or a combination of one or more equivalent antimicrobial agents that are insoluble in water or other fluid to be filtered. It is important that the antimicrobial agent not leach into the water or the fluid being filtered during the filtration process. The above-mentioned antimicrobial agents or equivalent ones that are insoluble in water, and are safe to use in drinking water and food related applications, can be used in this invention.
The preparation of concentrate of antimicrobial agent requires taking into consideration the thermoplastic properties of the main constituent of the porous sintered filter. Thermoplastic polymer for the concentrate of antimicrobial agent is chosen so that its melt flow index is greater than that of the main thermoplastic polymer, in order for the former to uniformly spread over all the surfaces of the sintered filter. In selecting these two thermoplastic polymers, consideration also must be given to their melting or softening temperatures, in case they are chemically dissimilar.
Typically a 10% to 20% concentrate by weight of the antimicrobial agent is prepared in the second thermoplastic polymer by a processing method such as: twin-screw extrusion, pelletizing and milling to size; or forming a mixture of a solution or emulsion of antimicrobial agent in a plasticizer. In order to ensure that this concentrate is homogeneously distributed in the mixture, its particle size is closely matched with that of the first thermoplastic polymer particles. The concentration of antimicrobial agent can be from 5% up to 80%, a preferable range is from 10% to 50%, but the optimum range of concentration is 10% to 20%. The let-down ratio of the concentrate into the main thermoplastic is determined by the concentration of the antimicrobial agent in the polymer concentrate and the concentration of the antimicrobial agent desired in the final sintered filter. Let-down ratios of from 1 to 1000, more typically 20 to 100, are used. A thermoplastic concentrate of additive such as this is diluted by addition of a preselected amount of primary thermoplastic polymer to achieve the final desired concentration of additive. Let-down ratio is the numerical value of dilution required to achieve the end concentration. A let-down ration of 20 would mean that one part of concentrate was diluted with 19 parts of primary thermoplastic polymer. Typically, the concentration of the antimicrobial additive based on the final weight of the sintered porous filter is in the range of approximately 50-20,000 ppm (parts per million) or 0.0005% to 2.0 percent by weight. Preferably a concentration of 1,000-5,000 ppm of antimicrobial additive is used, based on the weight of the final sintered porous filter, or 0.1 to 0.5 percent by weight.
The antimicrobial sintered porous filter of this invention can be used in the treatment of potable water. In many underdeveloped countries there is either a lack of infrastructure for municipally treated drinking water, or it exists in less than an adequate state. Under such conditions, it is necessary to have an over-head tank that is located on the roof of a building to store the water that is supplied, either intermittently by the municipalities, or by wells. Water in such tanks can become stagnant and subject to bacterial growth. It has now been found that the use of the antimicrobial sintered porous filter of this invention can eliminate the need to chlorinate the water and prevent the growth of bacteria in it. Simply by installing the invented filters on the outlet and inlet of the tank, drinking water was found to be devoid of detectable Coliform bacteria.
The antimicrobial sintered porous filter of this invention has also been used in water fount solutions for single or multi-station printing presses, either sheet or web fed, that use a water recirculation tank/system to filter/treat the recycled water. This water is subject to growth of bacteria and algae requiring frequent shut downs and clean ups. With the use of the invented filter this recycled water has been maintained free of microbial growth for very extended times such as 8 to 10 weeks, compared to less than one week before use of the invented filter.
A typical home or office humidifier draws ambient air and passes it through a moisture-laden wick filter and emits the resultant moist air back into the room or office. In these humidifiers, where water can be stagnant in some part of humidifier for extended periods, there can be the growth of undesirable bacteria such as Legionella pneumophilia and various types of algae. These microorganisms then can be emitted in the moist air causing serious danger to human respiratory health. The use of the invented antimicrobial sintered porous filter to treat the water to eliminate the bacteria before emitting it in the atmosphere can prevent aggravation of various allergies and respiratory diseases of human beings and animals, including pets.
Antimicrobial sintered porous filters of this invention can also be used in a spa. The current spa filter typically removes sediment from the water but is subject to severe microbiological growth. This necessitates addition and maintenance of high levels of chemical disinfectants such as chlorine. Use of antimicrobial sintered porous filters allows spa filters to avoid being a source of microbial growth and hence maintain more hygienic conditions in the spa filter and spa.
Water Coolers, where an inverted bottle sits atop a device that dispenses hot and/or cold water, are extensively used by commercial offices as well as by other consumers. Currently commercial filters are available that remove chlorine, taste and odor from the water contained in the bottle, using granulated activated carbon. The main disadvantage of such filter is the constant release of fine particulate carbon into the water and the growth of heterotrophic bacteria in the carbon, which creates bad taste in the water. The antimicrobial sintered porous filter of this invention overcomes both of these disadvantages as well as adding new features to this filter that were not possible before.
The principal object of the present invention is to provide an improved filter for purification of liquids.
Another object of this invention is to provide a method of making an antimicrobial sintered porous plastic filter.
Another object of this invention is to provide an antimicrobial sintered porous filter for filtration and purification of drinking water.
Another object of the invention is to provide apparatus for effective filtration and purification of water in a roof-top water storage tank, in printing presses, in spas, and in home and office humidifier and water cooler applications.
Another object of the invention is to provide a sintered porous thermoplastic filter for the treatment of fluids such as drinking water, fruit juices, oils, alcoholic beverages etc.
Another object of the invention is to provide a sintered porous thermoplastic filter for use in recirculation system of single or multi-station printing presses that are either sheet or web fed.
A further object of the invention is to provide a sintered porous thermoplastic filter for use in over-head rooftop water storage tanks to treat the water.
Another object of the invention is to provide a sintered porous thermoplastic filter for use in the treatment of water under gravity or pressure head of less than 10 psi.
Another object of the invention is to provide a sintered porous thermoplastic filter for use in the treatment of water under the pressure head of 10 to 500 psi.
Another object of the invention is to provide a sintered porous thermoplastic filter for use in air humidifiers.